All-electronic Nanosecond-resolved Scanning Tunneling Microscopy: Facilitating the Investigation of Single Dopant Charge Dynamics.

The miniaturization of semiconductor devices to scales where small numbers of dopants can control device properties requires the development of new techniques capable of characterizing their dynamics. Investigating single dopants requires sub-nanometer spatial resolution, which motivates the use of scanning tunneling microscopy (STM). However, conventional STM is limited to millisecond temporal resolution. Several methods have been developed to overcome this shortcoming, including all-electronic time-resolved STM, which is used in this study to examine dopant dynamics in silicon with nanosecond resolution. The methods presented here are widely accessible and allow for local measurement of a wide variety of dynamics at the atomic scale. A novel time-resolved scanning tunneling spectroscopy technique is presented and used to efficiently search for dynamics.

Time-resolved single dopant charge dynamics in silicon.

As the ultimate miniaturization of semiconductor devices approaches, it is imperative that the effects of single dopants be clarified. Beyond providing insight into functions and limitations of conventional devices, such information enables identification of new device concepts. Investigating single dopants requires sub-nanometre spatial resolution, making scanning tunnelling microscopy an ideal tool. However, dopant dynamics involve processes occurring at nanosecond timescales, posing a significant challenge to experiment. Here we use time-resolved scanning tunnelling microscopy and spectroscopy to probe and study transport through a dangling bond on silicon before the system relaxes or adjusts to accommodate an applied electric field. Atomically resolved, electronic pump-probe scanning tunnelling microscopy permits unprecedented, quantitative measurement of time-resolved single dopant ionization dynamics. Tunnelling through the surface dangling bond makes measurement of a signal that would otherwise be too weak to detect feasible. Distinct ionization and neutralization rates of a single dopant are measured and the physical process controlling those are identified.

Time-Resolved Imaging of Negative Differential Resistance on the Atomic Scale.

Negative differential resistance remains an attractive but elusive functionality, so far only finding niche applications. Atom scale entities have shown promising properties, but the viability of device fabrication requires a fuller understanding of electron dynamics than has been possible to date. Using an all-electronic time-resolved scanning tunneling microscopy technique and a Green's function transport model, we study an isolated dangling bond on a hydrogen terminated silicon surface. A robust negative differential resistance feature is identified as a many body phenomenon related to occupation dependent electron capture by a single atomic level. We measure all the time constants involved in this process and present atomically resolved, nanosecond time scale images to simultaneously capture the spatial and temporal variation of the observed feature.

Evaluating angular ion current density for atomically defined nanotips.

In this paper we investigate methods to characterize angular current density from atomically defined gas field ion sources. We show that the ion beam emitted from a single apex atom is described by a two-dimensional Gaussian profile. Owing to the Gaussian shape of the beam and the requirement to collect the majority of the ion current, fixed apertures have inhomogeneous illumination. Therefore, angular current density measurements through a fixed aperture record averaged angular current density. This makes comparison of data difficult as averaged angular current density depends on aperture size. For the same reasons, voltage normalization cannot be performed for fixed aperture measurements except for aperture sizes that are infinitely small. Consistent determination of angular current density and voltage normalization, however, can be achieved if the beam diameter as well as total ion current are known. In cases where beam profile cannot be directly imaged with a field ion microscope, the beam profile could be extracted from measurements taken at multiple acceleration voltages and/or with multiple aperture sizes.

Single-electron dynamics of an atomic silicon quantum dot on the H-Si(100)-(2×1) surface.

Here we report the direct observation of single electron charging of a single atomic dangling bond (DB) on the H-Si(100)-2×1 surface. The tip of a scanning tunneling microscope is placed adjacent to the DB to serve as a single-electron sensitive charge detector. Three distinct charge states of the dangling bond--positive, neutral, and negative--are discerned. Charge state probabilities are extracted from the data, and analysis of current traces reveals the characteristic single-electron charging dynamics. Filling rates are found to decay exponentially with increasing tip-DB separation, but are not a function of sample bias, while emptying rates show a very weak dependence on tip position, but a strong dependence on sample bias, consistent with the notion of an atomic quantum dot tunnel coupled to the tip on one side and the bulk silicon on the other.

Tip apex shaping of gas field ion sources.

A procedure to control W(111) tip shape during etching to a single atom is described. It is demonstrated that the base of a single atom tip (SAT) can be shaped in order to alter the final operating voltage and emission opening angle of single atom tips for use as gas field ion sources or electron cold field emission sources. The operating voltages for single atom tips varied between 5 and 17kV during helium ion beam generation. The emission properties of SATs were evaluated by fitting SAT images and measuring the full width at half maximum (FWHM) of the helium ion images. The FWHM is related to the linear opening angle and was evaluated as a function of SAT operating voltage. The results show that a forward focussing effect is observed such that the spot size decreases faster than is expected solely from an acceleration effect, indicating an affect from the tip shape. These results have consequences in designing gas field ion sources where etching is used to prepare the emitter.

Photolysis and thermolysis of pyridyl carbonyl azide monolayers on single-crystal platinum.

The photochemical and thermal reactivity of a number of acyl azide-substituted pyridine compounds, namely nicotinyl azide, isonicotinyl azide, picolinyl azide and dinicotinyl azide with investigated as saturated monolayers on a single-crystal Pt(111) surface in an ultrahigh vacuum chamber. Multilayers of the substrates exhibited a maximum rate of desorption at 270 K, above which, stable saturated monolayers formed as characterized by reflection-absorption infrared spectroscopy by observation of C=O and N3 bands at 1700 cm(-1), and 2100 and 1300 cm(-1) respectively. The monolayers were stable up to 400 K. Photolysis of the monolayer (or heating above 400 K) results in the formation of the respective isocyanate intermediate after loss of nitrogen as evidenced by the appearance of a new infrared band at 2260 cm(-1) with concomitant loss of the azide bands. The resulting isocyanate saturated monolayer is stable in absence of nucleophiles, but can be quenched with appropriate nucleophiles.

Field ion microscope evaluation of tungsten nanotip shape using He and Ne imaging gases.

Field ion microscopy (FIM) using neon imaging gas was used to evaluate a W(111) nanotip shape during a nitrogen assisted etching and evaporation process. Using appropriate etching parameters a narrow ring of atoms centered about the tip axis appears in a helium generated image. Etching of tungsten atoms continues exclusively on the outside of this well-defined ring. By replacing helium imaging gas with neon, normally inaccessible crystal structure of a tip apex is revealed. Comparison of the original W(111) tip (before etching) and partly etched tip shows no atomic changes at the tip apex revealing extraordinarily spatially selective etching properties of the etching process. This observation is an important step towards a detailed understanding of the nitrogen assisted etching and evaporation process and will lead to better control over atomically defined tip shapes.

Creation and recovery of a W(111) single atom gas field ion source.

Tungsten single atom tips have been prepared from a single crystal W(111) oriented wire using the chemical assisted field evaporation and etching method. Etching to a single atom tip occurs through a symmetric structure and leads to a predictable last atom unlike etching with polycrystalline tips. The single atom tip formation procedure is shown in an atom by atom removal process. Rebuilds of single atom tips occur on the same crystalline axis as the original tip such that ion emission emanates along a fixed direction for all tip rebuilds. This preparation method could be utilized and developed to prepare single atom tips for ion source development.

Indications of field-directing and self-templating effects on the formation of organic lines on silicon.

It has previously been shown that multimolecular organic nanostructures form on H-Si(100)-2×1 via a radical mediated growth process. In this mechanism, growth begins through the addition of a molecule to a silicon surface dangling bond, followed by the abstraction of a neighboring H atom and generation of a new dangling bond on the neighboring site. Nanostructures formed by this mechanism grow along one edge of a dimer row. Here, we explored the possibility of using lithographically prepared, biased metal contacts on the silicon surface to generate an electric field that orients molecules during the growth process to achieve growth in the perpendicular-to-row direction. The formation of some nanostructures in a direction that was nearly perpendicular to the dimer rows was achieved, whereas such features were not formed in the absence of the field. Analysis of the scanning tunneling microscopy images suggests that the formation of these nanostructures may involve self-templating effects in addition to dangling bond diffusion rather than a straightforward addition∕abstraction mechanism. These initial results offer some indication that a molecular pattern writer can be achieved.

Tunnel coupled dangling bond structures on hydrogen terminated silicon surfaces.

We study both experimentally and theoretically the electronic behavior of dangling bonds (DBs) at a hydrogen terminated Si(100)-2×1 surface. Dangling bonds behave as quantum dots and, depending on their separation, can be tunnel coupled with each other or completely isolated. On n-type highly doped silicon, the latter have a net charge of -1e, while coupled DBs exhibit altered but predictable filling behavior derived from an interplay between interdot tunneling and Coulomb repulsion. We found good correlation between many scanning tunneling micrographs of dangling bond structures and our theoretical results of a corresponding extended Hubbard model. We also demonstrated chemical methods to prevent tunnel coupling and isolate charge on a single dangling bond.

Charge control of surface dangling bonds using nanoscale Schottky contacts.

Titanium silicide (TiSi2) nanoscale Schottky contacts were prepared on hydrogen-terminated n-type Si (100) surfaces. The Schottky contact created a region of upward band bending surrounding the TiSi2 contacts. The surface band bending was observed as a sloping surface depression using the scanning tunneling microscope. Scanning tunneling spectroscopy measurements also show shifted I/V data consistent with upward band bending. Charge control of dangling bonds was accomplished through a distance relationship between the dangling bond and the TiSi2 contact. The lowered chemical potential in the near contact region removes the ability of dangling bonds to become negatively charged while dangling bonds outside the close contact region remain fully charged. Methods to actively control dangling bond charge states are discussed.

Controlled coupling and occupation of silicon atomic quantum dots at room temperature.

It is demonstrated that the silicon atom dangling bond (DB) state serves as a quantum dot. Coulomb repulsion causes DBs separated by less, similar2 nm to exhibit reduced localized charge, which enables electron tunnel coupling of DBs. Scanning tunneling microscopy measurements and theoretical modeling reveal that fabrication geometry of multi-DB assemblies determines net occupation and tunnel coupling strength among dots. Electron occupation of DB assemblies can be controlled at room temperature. Electrostatic control over charge distribution within assemblies is demonstrated.

Theoretical and spectroscopic study of the reaction of diethylhydroxylamine on silicon(100)-2 x 1.

Incorporating diversity into structures constructed from the organic modification of silicon surfaces requires the use of molecules that contain multiple substituents of different types. In this work we examine the possible dissociation pathways of diethylhydroxylamine (DEHA, (C(2)H(5))(2)NOH) on the surface of clean silicon(100)-2x1 using cluster and planewave computational methods and high resolution electron energy loss spectroscopy. Our computational results show that DEHA initially forms a strongly-bound complex with the surface via a dative N-Si bond. A low-barrier O-H bond scission then occurs yielding a surface silicon dimer capped by the (C(2)H(5))(2)NO and H fragments. Calculated and measured vibrational spectra support the computed reaction mechanism.

Detailed studies of molecular conductance using atomic resolution scanning tunneling microscopy.

Atomically resolved scanning tunneling microscopy and spectroscopy (STM/STS) have been used to carefully examine the relationship between molecular conductivity and the adsorption state of various organic molecules on silicon surfaces. We show that the particular configuration of styrene and cyclopentene molecules on silicon affects the conductivity of the molecules. Detailed correlation of STM images with point specific current-voltage spectroscopy reveal that observed negative peaks are due to random configuration changes driven by inelastically scattered electrons and not due to tuned alignment of molecule and electrode levels. These random processes, which include molecular rearrangement, desorption, and/or decomposition occur with increasing frequency at larger voltage and current settings.

Linear nanostructure formation of aldehydes by self-directed growth on hydrogen-terminated silicon(100).

The self-directed growth of organic molecules on silicon surfaces allows for the rapid, parallel production of hybrid organic-silicon nanostructures. In this work, the formation of benzaldehyde- and acetaldehyde-derived nanostructures on hydrogen-terminated H-Si(100)-2x1 surface is studied by scanning tunneling microscopy in ultrahigh vacuum and by quantum mechanical methods. The reaction is a radical-mediated process that binds the aldehydes, through a strong Si-O covalent bond, to the surface. The aldehyde nanostructures are generally composed of double lines of molecules. Two mechanisms that lead to double line growth are elucidated.

Field regulation of single-molecule conductivity by a charged surface atom.

Electrical transport through molecules has been much studied since it was proposed that individual molecules might behave like basic electronic devices, and intriguing single-molecule electronic effects have been demonstrated. But because transport properties are sensitive to structural variations on the atomic scale, further progress calls for detailed knowledge of how the functional properties of molecules depend on structural features. The characterization of two-terminal structures has become increasingly robust and reproducible, and for some systems detailed structural characterization of molecules on electrodes or insulators is available. Here we present scanning tunnelling microscopy observations and classical electrostatic and quantum mechanical modelling results that show that the electrostatic field emanating from a fixed point charge regulates the conductivity of nearby substrate-bound molecules. We find that the onset of molecular conduction is shifted by changing the charge state of a silicon surface atom, or by varying the spatial relationship between the molecule and that charged centre. Because the shifting results in conductivity changes of substantial magnitude, these effects are easily observed at room temperature.

Protection-deprotection chemistry to control styrene self-directed line growth on hydrogen-terminated Si(100).

TEMPO, 2,2,6,6-tetramethylpiperidinyloxy, was used in a series of protection-deprotection chemical reactions in order to gain single molecule-level control over the extent of styrene line growth on hydrogen-terminated Si(100). The mechanism involves the reaction of TEMPO with the dangling bond at the end of individual styrene lines. The TEMPO cap protects the dangling bond from further reaction with styrene resulting in the termination of line growth. TEMPO is then selectively removed from desired lines, deprotecting the dangling bond, using the scanning tunneling microscope. Further exposure of the surface to styrene ensures that only the deprotected areas continue to grow while the protected lines do not. All lines can then be capped with TEMPO, and this allows for the generation of stable styrene lines of varying lengths.